High energy density li-ion battery electrode materials and cells

ABSTRACT

A method of preparing a high capacity nanocomposite cathode of FeF 3  in carbon pores may include preparing a nanoporous carbon precursor, employing electrochemistry or solution chemistry deposition to deposit Fe particles in the carbon pores, reacting nano Fe with liquid hydrofluoric acid to form nano FeF 3  in carbon, and milling to achieve a desired particle size.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of co-pending U.S.Nonprovisional application Ser. No. 13/588,082, filed on Aug. 17, 2012,and which claims priority to and the benefit of U.S. ProvisionalApplication No. 61/603,506 filed on Feb. 27, 2012, now expired, thecontents of which are hereby incorporated herein by reference in theirentireties.

TECHNICAL FIELD

Example embodiments generally relate to battery technology and, moreparticularly, relate to a mechanism for providing high energy densityelectrodes for batteries.

BACKGROUND

Batteries are electrochemical cells that convert stored chemical energyinto electrical energy. Batteries have been desirable sources ofelectrical energy due to the fact that they can deliver energy withoutthe mobility restrictions provided by a corded connection to mains powersystems. Two main types of batteries include primary (or disposable)batteries and secondary (or rechargeable) batteries. Primary batteriesare generally able to produce current immediately after they areassembled. However, primary batteries are intended to be discarded aftertheir charge is depleted since the chemical reactions utilized thereinare generally not reversible. Secondary batteries must generally becharged before use. However, after charge depletion they can berecharged since the chemical reactions utilized therein are reversible.

As different types of batteries have been developed and improved overthe years, research has continued to focus on improving energy density,durability and safety, while decreasing cost. Reduction or eliminationof memory effect, a phenomenon whereby batteries gradually lose theirmaximum energy capacity if they are repeatedly recharged after beingonly partially discharged, has also been a focus of many past researchefforts.

One of the top performing rechargeable batteries that has evolved fromthe efforts described above has been the lithium-ion (Li-ion) battery.The Li-ion battery generally provides a relatively high energy density,no memory effect, and relatively low charge loss when not in use. Due toits performance capabilities, Li-ion batteries have been preferred formany applications including the provision of power to satellites andother payloads that are to be used in space missions. The relativelyhigh energy density provided by Li-ion batteries means that space boundsatellites or payloads may be effectively powered with less weight.However, the relatively high cost of Li-ion batteries may significantlyadd to the cost of such batteries when they are used in spaceapplications.

BRIEF SUMMARY OF SOME EXAMPLES

Accordingly, some example embodiments may enable the provision of Li-ionbatteries with even higher energy densities. Thus, the same electricalcapacity may be provided with significantly less weight and cost. Someexample embodiments may provide scalable methods for creatingnanostructured electrode materials that improve the performance ofLi-ion batteries.

In one example embodiment, a method of providing electrode materials fora battery cell is provided. The method may include preparing a highcapacity nanocomposite cathode of FeF₃. In some cases, the high capacitynanocomposite cathode of FeF₃ may be prepared in carbon pores bypreparing a nanoporous carbon precursor, employing electrochemistry orsolution chemistry deposition to deposit Fe particles in the carbonpores, reacting nano Fe with liquid hydrofluoric acid to form nano FeF₃in carbon, and milling to achieve a desired particle size. The methodmay further include preparing a high capacity nanocomposite anode of Cuand Si by creating a Cu: Si interface via electrodeposition orphysically forming Cu around Si by milling, and annealing to enhanceatomic intermixing. The method may further include combining the highcapacity nanocomposite cathode with the high capacity nanocompositeanode for a high energy density Lithium-ion battery cell.

According to another example embodiment, a method of preparing a highcapacity nanocomposite cathode of FeF₃ in carbon pores is provided. Themethod may include preparing a nanoporous carbon precursor, employingelectrochemistry or solution chemistry deposition to deposit Feparticles in the carbon pores, reacting nano Fe with liquid hydrofluoricacid to form nano FeF₃ in carbon, and milling to achieve a desiredparticle size.

According to another example embodiment, a method of providing electrodematerials for a battery cell is provided. The method may includepreparing a high capacity nanocomposite cathode of FeF₃ by reacting ironnitrate nonahydrate with hydrofluoric acid to yield hydrated ironfluoride, and heating the hydrated iron fluoride in argon. The methodmay further include preparing a high capacity nanocomposite anode ofcopper and silicon, and combining the high capacity nanocompositecathode with the high capacity nanocomposite anode for a high energydensity Lithium-ion battery cell.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

Having thus described the invention in general terms, reference will nowbe made to the accompanying drawings, which are not necessarily drawn toscale, and wherein:

FIG. 1 is a block diagram of a conventional Li-ion battery;

FIG. 2 illustrates a block diagram of a Li-ion battery employingnanomaterial electrodes according to an example embodiment;

FIG. 3 illustrates an example method of creating a high capacity Li-ionbattery having high capacity electrodes according to an exampleembodiment;

FIG. 4 illustrates a more specific example method of creating a highcapacity nanocomposite cathode in which solution chemistry and inertannealing is employed for deposition of the Fe in pores of carbon;

FIG. 5 illustrates a more specific example method of creating a highcapacity nanocomposite cathode in which electrochemistry and solutionchemistry, along with inert annealing, are employed for deposition ofthe Fe in pores of carbon;

FIG. 6 illustrates a more specific method of preparing an anode materialfor a high capacity battery according to an example embodiment;

FIG. 7 illustrates a more specific method of preparing an anode materialfor a high capacity battery according to another example embodiment.

FIG. 8 illustrates via scanning electron microscopy the iron (III)fluoride particles synthesized using the described technique of reactingiron (III) nitrate nonahydrate (Fe(NO₃)₃.9H₂O) with hydrofluoric acid(HF) and then heat treating the product in argon to yield the finalanhydrous material according to an example embodiment;

FIG. 9 demonstrates the FeF₃ material through energy dispersivespectroscopy according to an example embodiment;

FIG. 10 is a flowchart of the synthesis of copper-coated siliconnanopowder for use as anode material in Li-ion batteries according to anexample embodiment;

FIG. 11 shows the x-ray diffraction patterns of the Si/Cu anode materialthrough the three discrete process steps described by the flowchart inFIG. 10 according to an example embodiment; and

FIG. 12, through energy dispersive spectroscopy, demonstrates theexistence of a thin layer of copper remains bonded to the siliconparticles after the final etch step in the anode synthesis procedureaccording to an example embodiment.

DETAILED DESCRIPTION

Some example embodiments now will be described more fully hereinafterwith reference to the accompanying drawings, in which some, but not allexample embodiments are shown. Indeed, the examples described andpictured herein should not be construed as being limiting as to thescope, applicability or configuration of the present disclosure. Rather,these example embodiments are provided so that this disclosure willsatisfy applicable legal requirements. Like reference numerals refer tolike elements throughout.

Some example embodiments may enable the provision of Li-ion batterieswith high energy densities by employing nanostructured electrodematerials. Thus, for example, the same electrical capacity may beprovided with significantly less weight and cost. It also follows that,for example in connection with satellite/payload applications for spacemissions, increased energy density may provide significant savings incost per unit of weight. As an example, if energy density may beincreased by 3.5 times that of a conventional battery, up to $3.5M/5000kg satellite may be saved. Increased capabilities may also enable spacecustomers to develop higher power spacecraft buses and more capablepayloads while also enabling more efficient nanosatellite missions.

Some example embodiments may represent a paradigm shift fromconventional intercalation based Li-ion storage electrode materials todisplacement reaction and alloying type, ultra-high, near theoreticalLi-ion storage nanomaterials based on metal fluoride:carbon compositecathode nanomaterials and Cu: Si based anode nanomaterials. Employingnanostructured materials may increase the surface area and decreasediffusion lengths (e.g., decreasing target pore sizes in host materialsuch as carbon and also decreasing particle size to improve the ratio ofFeF₃ to C). Some embodiments may further employ materials synthesis tooptimize specific material compositions for maximum energy density(e.g., employing solution chemistry, electrochemistry and/or mechanicalmilling techniques. Some embodiments may also involve materialscharacterization such as microscopy, particle size analysis, pore sizeanalysis, X-ray diffraction for phase analysis, and electrochemicalcharacterization. Example embodiments may, in some cases, also providefor scalable manufacturing of both anode and cathode materials for usein the high energy density batteries described herein, while maintaininghigh reaction kinetics at room temperature. Thus, some embodiments mayenable FeF₃ to be generated in-situ inside pores of a carbon host, andmay enable distribution and size of the FeF₃ to be tailored to decreasediffusion lengths and improve electrochemical activity at roomtemperature.

FIG. 1 is a block diagram of a conventional Li-ion battery. The battery10 may include an anode 12 and a cathode 14. As shown in FIG. 1, thematerial employed for the anode 12 may be graphite. Using such materialmay result in a capability of delivering about 225-300 mAh/g and 0.05 Vvs Li/Li⁺. The material employed for the cathode 14 may beLiNi_(x)Co_(1-x)O₂. Using such material may result in a capability ofdelivering about 150-200 mAh/g and 3.65 V vs Li/Li⁺. Energy densitydeliverable by the battery 10 may be about 205 Wh/kg. FIG. 2 illustratesa block diagram of a Li-ion battery 20 employing nanomaterial electrodesaccording to an example embodiment. As shown in FIG. 2, the battery 20may include an anode 22 and a cathode 24. As shown in FIG. 2, thematerial employed for the anode 22 may be a nano Cu: Si composite. Usingsuch material may result in a capability of delivering about 2800 mAh/gand 0.2 V vs Li/Li⁺. The material employed for the cathode 24 may benano FeF₃:C composite. Using such material may result in a capability ofdelivering about 300 mAh/g and 2.5 V vs Li/Li⁺. Energy densitydeliverable by the battery 10 may be about 525-700 Wh/kg. Thus, about3.5 times improvement in energy density may be achievable by employingnanomaterials for the electrodes instead of using conventional Li-ionbattery techniques.

Nano FeF₃:C nanocomposite bulk cathode material has excellent potentialfor exhibiting high specific capacities in the range of 600 mAh/g.Making the material nano-scale in nature may be useful for reducingLi-ion diffusion distances within the material and may also make thematerial more facile for reverse displacement with respect to thereaction: 3LiF+Fe→FeF₃+3Li⁺. Nano-scale materials may also exhibitimproved accommodation of strain during electrochemical cycling due tothe large surface area to volume ratio inherent in the nanomaterial.Some embodiments may enable generation of FeF3 nanoparticles in-situwithin nanopores of a porous carbon host matrix so that electrochemicalcycling of a FeF₃ based cathode is possible, even at temperatures below70 degrees C. Accordingly, a scalable, high energy density drop-inreplacement cathode material for LiCoO₂ or other conventional lowcapacity cathode materials may be producible.

In an example embodiment, high capacity cathode material fabrication maybe accomplished by employing electrochemistry and/or solution chemistry.In either case, a porous carbon precursor solution may initially beobtained. Electrochemistry or solution chemistry deposition techniquesmay then be employed to deposit iron (Fe) particles in the pores ofcarbon. Thereafter, nano Fe may be reacted with liquid HF to form nanoFeF₃ in carbon and the result may be milled. Cathode material fabricatedfor high energy capacity may then be used in connection with anodematerial fabricated for high energy capacity. FIG. 3 illustrates anexample method of creating a high capacity Li-ion battery having highcapacity electrodes according to an example embodiment. The method ofFIG. 3 may further include operations for provision of high capacitycathode material for combination with high capacity anode material toform a high energy density Li-ion battery according to an exampleembodiment. However, it should be appreciated that there may be multiplespecific sequences within the more general method of FIG. 3 forgenerating both the high capacity cathode material and the high capacityanode material. FIG. 4 illustrates a more specific example method ofcreating a high capacity nanocomposite cathode in which solutionchemistry and inert annealing is employed for deposition of the Fe inpores of carbon. FIG. 5 illustrates a more specific example method ofcreating a high capacity nanocomposite cathode in which electrochemistryand solution chemistry, along with inert annealing, are employed fordeposition of the Fe in pores of carbon. FIG. 6 illustrates a morespecific method of preparing an anode material for a high capacitybattery according to an example embodiment. FIG. 7 illustrates a morespecific method of preparing an anode material for a high capacitybattery according to another example embodiment.

Referring now to FIG. 3, the method includes preparing a high capacitynanocomposite cathode material (e.g., such as cathode 24 of FIG. 2) ofFeF₃ in carbon pores at operation 100, which may accomplished viaoperations including preparing a nanoporous carbon precursor atoperation 110. In some embodiments, for example, carbon aerogel or anion exchange resin such as a Purolite macronet material may be employedand infiltrated with an iron precursor solution such as iron chloride oriron nitrate. The method further includes employing electrochemistry orsolution chemistry deposition to deposit Fe particles in the pores ofcarbon at operation 120. At operation 130, the method includes reactingnano Fe with liquid HF to form nano FeF₃ in carbon. Thereafter, themethod includes milling to achieve a desired or appropriate particlesize at operation 140. The milling may be, for example, mechanicalmilling or ball milling utilized to decrease the particle size. In somecases, the method may further include operation 150, which may includecharacterizing the electrochemical and/or morphological properties ofthe resultant material. Thus, for example, the preparation of thecathode material may conclude with screening the resultant material forits morphological and electrochemical properties.

Operation 100 (which may include some or all of operations 110 through150) may represent a method for preparing a high capacity nanocompositecathode. The method of FIG. 3 may further include preparing a highcapacity anode material at operation 160, which may include creating aCu: Si interface via electrodeposition or physically forming Cu aroundSi by milling at operation 170 and annealing to enhance atomicintermixing at operation 180. Operation 160 may further includecharacterizing the resultant material for electrochemical andmorphological properties at operation 190. The method may then concludeby combining the high capacity nanocomposite cathode (e.g., generatedvia operations 110-150) with a high capacity nanocomposite anode (e.g.,generated via operation 160-190) at operation 200 to generate a highenergy density Li-ion battery cell.

As indicated above, the method of FIG. 3 may be performed by employingelectrochemistry or solution chemistry deposition techniques to generatethe cathode material. In this regard, as shown in FIG. 4, operation 120may instead include specific operations associated with solutionchemistry techniques. In this regard, for example, operation 120 may bereplaced more specifically with operation 122 including infiltrating thecarbon pores with an Fe precursor solution and operation 124 includingapplying heat treatment in an inert atmosphere to leave behind nano Feparticles in the pores of carbon. As such, for example, infiltratedcarbon precursor (from operation 122) may be heat treated to an elevatedtemperature of about 600 to about 1000 degrees C. in an inert atmosphereto yield Fe filled pores in a carbon host. The powder may then bereacted with hydrofluoric (HF) acid to generate nano FeF₃ in the pores(in operation 130) after which time the above described milling process(of operation 140) may be initiated.

Alternatively, if an electrochemical deposition technique is preferred,operation 120 may instead include applying heat treatment in an inertatmosphere to form nanoporous carbon as shown in operation 126 of FIG.5. As such, for example, a porous carbon precursor (e.g., a carbonaerogel or ion exchange resin such as a Purolite macronet material) maybe immediately heat treated at an elevated temperature of about 600 toabout 1000 degrees C. in the inert atmosphere to yield a nanoporouscarbon host. Thereafter, at operation 128, Fe may be electrochemicallydeposited in the nanopores of carbon. Thus, for example, the powder maythen be collected, placed in a suitable metal mesh container, and placedin an iron based electrolyte bath. With an iron counter-electrode, themetal mesh container/porous carbon powder may be used as the workingelectrode and current may be applied to electrodeposit ironnanoparticles inside the pores of the porous carbon host. Following ironelectrodeposition, the iron:carbon powder may be placed in HF acid togenerate FeF₃ nanoparticles in the pores of the carbon host (inoperation 130) after which time the above described milling process (ofoperation 140) may be initiated.

In an example embodiment, anode material fabrication (e.g., inaccordance with operation 160) may be accomplished by employing eitherscalable electrochemistry based methods involving electrodeposition orby employing scalable, high energy mechanical milling based methods toform Cu around Si to form the Cu: Si interface. While an FeF₃ basedcathode material may be sufficient to exhibit reversible displacementreactions with all elements participating in the reaction, high energydensity anode materials may be produced using a slightly differentstrategy. For example, silicon (Si) may be employed as a high capacity“active” material and copper (Cu) may act as an adhesive or “glue” tohold the Si together during the potentially extreme (e.g., about 400%)volumetric expansion that occurs when Si alloys with Li. The expansionmay, in some cases, be so severe that if Si is cycled alone with noinactive “glue” phase, high initial capacity may be provided, but thecapacity may fade drastically after only several cycles due to thematerial undergoing cracking such that electrical contact with thecurrent collector is compromised. While the maximum theoretical capacityof lithiated silicon is about 3600 to about 4000 mAh/g, a parameterspace in the about 2000 to about 3000 mAh/g range may be explored foruse in connection with some embodiments by tailoring the percentage ofCu added to the Si and observing the effect on capacity retention as afunction of cycle number. Thus, some embodiments may provide for ascalable production of bulk silicon based anode powder as a drop-inreplacement anode material for graphite in conventional cells. Cu mayform an effective interface with amorphous Si thin films duringelectrochemical lithiation and delithiation. In thin film cases, testinghas shown that the interface may preserve the capacity for a finitenumber of cycles and it may be possible to achieve previouslyunattained, near theoretical, reversible capacity values of about 3500mAh/g for a Si based anode.

Thus, for example, alternative embodiments for performing operation 160may be employed. More specifically, some embodiments may employelectrodeposition when performing operation 170, while other exampleembodiments may employ milling to physically form Cu around Si whenperforming operation 170. FIG. 6 illustrates an example method ofpreparing an anode material for a high capacity battery (e.g., operation160 of FIG. 3) in which operation 170 is replaced with more specific suboperations. In this regard, as shown in FIG. 6, the method of thisexample embodiment includes preparing amorphous silicon nanoparticlesusing high energy mechanical milling at operation 171. At operation 172,powder that aggregates may then be placed in a fine metal meshcontainer. In some cases, the mechanical milling and placement of thepowder into the mesh container may be followed by an electrodepositionoperation. In this regard, a metal mesh/sample may be used as a workingelectrode and a thin Cu layer may be deposited on the Si nanoparticlesat operation 173. By placing aggregated, milled powder in a fine meshbasket (at operation 172) and electrodepositing a very thin film of Cuon the Si powder (at operation 173), a high quality interface betweenthe Cu and Si may be achieved to provide stabilization of very highspecific capacities. Electrochemical and morphological properties of theresultant material may then be characterized at operation 190 afterannealing (at operation 180).

An alternative method of preparing an anode material for a high capacitybattery may include the use of a “one-pot” synthesis approach in whichsilicon powder, copper powder, and a milling agent such as carbon blackare provided in various weight ratios at operation 175, as shown in FIG.7. The powders and milling agent may then be milled via high energymechanical milling to attempt to in-situ form a high quality Cu: Sinanocomposite at operation 177. A final annealing operation may then beperformed to enhance atomic intermixing at the Cu—Si interface in thenanomaterials at operation 180 and electrochemical and morphologicalproperties of the resultant material may then be characterized atoperation 190. The degree of intermixing may play a significant role indetermining the strength at the interface between the two materials. Byperforming operations 175 and 177 as specific sub operations ofoperation 170, the Cu: Si interface may be created by physically formingCu around Si using milling processes.

The potential benefit of improving the capacity of cathode and anodematerials to provide a high energy density Li-ion battery as provided inFIG. 2 may be projected by calculating the amount of active materialpresent in a conventional battery, keeping the total mass of anode andcathode materials the same, inserting the expected gravimetriccapacities of new anode and new cathode materials (i.e., materialsgenerated via the examples of FIGS. 4-7 such that the capacity of theanode equals the capacity of the cathode), solving for the expectedmasses of anode and cathode materials, calculating the new batterycapacity in Ah, multiplying by the average voltage of the new battery,and dividing by the total mass of the battery (kept the same for theconventional and new batteries). Thus, for example, the estimatedimprovement for a nanostructured electrode material battery (e.g., likethe one in FIG. 2) may be up to 3.5 times improvement relative to theexample shown in FIG. 1.

Table 1 below illustrates some parameters that may be employed inconnection with an example embodiment. However, it should be appreciatedthat other performance parameters may be achieved by alternativeembodiments. Thus, the parameters of Table 1 should be appreciated asnon-limiting examples. The first two columns of Table 1 relate toparameters of a conventional Li-ion battery and the last two columns(i.e., the two right-most columns) relate to corresponding parameters ofa high energy density Li-ion battery of an example embodiment.

TABLE 1 Total Capacity 370 Ah Total Capacity 1521-2031 Ah Total Weight6.67 kg Total Weight 6.67 kg Cathode Material LiNi_(1−x)Co_(x)O₂ CathodeMaterial Nano FeF₃:C Assumed Cathode 150-200 mAh/g Assumed Cathode 610mAh/g Specific Capacity Specific Capacity Average cathode 3.65 V vsLi/Li+ Average cathode 2.5 V vs Li/Li+ voltage voltage Calculated weightof 1.85-2.46 kg Calculated weight of 2.54-3.39 kg cathode materialcathode material Anode Material Graphite Anode Material Nano Cu:SiAssumed Anode 225-300 mAh/g Assumed Anode 2800 mAh/g Specific CapacitySpecific Capacity Average Anode 0.05 V vs Li/Li+ Average Anode 0.2 V vsLi/Li+ voltage voltage Calculated weight of 1.23-1.64 kg Calculutedweight 0.54-0.73 kg anode material anode material Total Electrode3.08-4.11 kg Total Electrode 3.08-4.11 kg Material Weight MaterialWeight Total Remaning 2.56-3.59 kg Total Remaining 2.56-3.59 kg Weight(packaging etc) Weight (packaging etc) Average Cell Voltage 3.6 VAverage Cell Voltage 2.3 V Energy Density 205 Wh/kg Energy Density525-700 Wh/kg

In order to manufacture a battery with high capacity electrodematerials, operations associated with refining particle size of theelectrode material using milling and sieving processes may be employed.Electrode material slurry preparation using polymer binders such aspolyvinylidiene fluoride or Teflon, carbon black, n-methyl pryollidinonesolvent, and the active material may also be employed. In some cases,electrode materials may be cast on a current collector such as copper oraluminum foils and a doctor blade or wire-wound rod may be employed toprepare a uniform height slurry. The solvent may be evaporated in acontrolled fashion and the anode and cathode foils may be wound togetherwith a separator such as, for example, a celgard typepolyethylene:polypropylene layered tortuous separator disposedtherebetween. The winding may be packaged in a can or other package andsealed using welding or other sealing processes. Contents may thereafterbe evacuated and the package may be backfilled with electrolyte andsealed.

In some embodiments, an alternative synthesis method to produce FeF₃ foruse as a cathode material for lithium-based batteries may be provided.Specifically, for example, iron (III) nitrate nonahydrate(Fe(NO₃)₃.9H₂O) may be reacted with hydrofluoric acid (HF). Thisreaction yields hydrated iron (III) fluoride (FeF₃.xH₂O). Heating thehydrated iron fluoride in argon (e.g., for two hours at 400° C.) mayyield a final nano-scale iron (III) fluoride (FeF₃) product, as shown inFIG. 8. This is chemically illustrated in the reaction below:

$\left. {{{{{Fe}\left( {NO}_{3} \right)}_{3} \cdot 9}H_{2}O} + {HF}}\rightarrow{{{{FeF}_{3} \cdot {xH}_{2}}O}\overset{{400{{^\circ}C}},\mspace{11mu} {2\mspace{11mu} {{hr}.}},\; {Ar}}{\rightarrow}{FeF}_{3}} \right.$

In addition to FIG. 8, data demonstrating the successful synthesis ofFeF₃ is shown in FIG. 9, by energy dispersive x-ray spectroscopy revealsthe elemental existence of iron and fluorine in the final synthesizedproduct.

In some embodiments, a procedure for plating a thin layer of copper onsilicon nanopowder is also provided. FIG. 10 illustrates a flowchartdetailing example synthesis steps associated with the synthesis ofcopper-coated silicon nanopowder for use as anode material in Li-ionbatteries. The three main steps of the copper plating approach are: 1)electroless plating of copper on silicon nanopowder at operation 200, 2)annealing the Cu/Si nanopowder at operation 210, and 3) etching excessCu from the surface of the Cu/Si nanopowder at operation 220. Furtherdetails that may be employed in connection with one example embodimentof Cu/Si anode synthesis are also given in FIG. 10. However, it shouldbe appreciated that the details of FIG. 10 are examples and notnecessarily the only detailed steps that may be employed for anodesynthesis in alternative embodiments.

FIG. 11 shows x-ray diffraction patterns at the conclusion of each ofoperations 200, 210 and 220 to illustrate the existence of the synthesisof a Cu/Si nanoscale anode material in an example embodiment. In FIG.11, the electroless Cu plating of Si nanopowder corresponds to pattern250, the annealing step corresponds to pattern 260, and the copperetching step corresponds to pattern 270. The pattern 250 reveals theexistence of silicon and copper peaks. The pattern 260 shows that thesilicon peaks remain, but copper (II) oxide is formed during theannealing step. Analysis of the pattern 270 shows only silicon peaks (nocopper) on the post-etched samples. However, the EDS (Energy-Dispersivex-ray Spectroscopy—a surface sensitive materials characterizationtechnique) pattern of the post-etched sample (FIG. 12) shows a largesilicon peak (confirming the pattern 270) as well as the existence ofcopper. This demonstrates that the procedure described herein verifiesthe creation of silicon nanoparticles coated with a thin layer ofcopper.

Many modifications and other embodiments of the inventions set forthherein will come to mind to one skilled in the art to which theseinventions pertain having the benefit of the teachings presented in theforegoing descriptions and the associated drawings. Therefore, it is tobe understood that the inventions are not to be limited to the specificembodiments disclosed and that modifications and other embodiments areintended to be included within the scope of the appended claims.Moreover, although the foregoing descriptions and the associateddrawings describe exemplary embodiments in the context of certainexemplary combinations of elements and/or functions, it should beappreciated that different combinations of elements and/or functions maybe provided by alternative embodiments without departing from the scopeof the appended claims. In this regard, for example, differentcombinations of elements and/or functions than those explicitlydescribed above are also contemplated as may be set forth in some of theappended claims. In cases where advantages, benefits or solutions toproblems are described herein, it should be appreciated that suchadvantages, benefits and/or solutions may be applicable to some exampleembodiments, but not necessarily all example embodiments. Thus, anyadvantages, benefits or solutions described herein should not be thoughtof as being critical, required or essential to all embodiments or tothat which is claimed herein. Although specific terms are employedherein, they are used in a generic and descriptive sense only and notfor purposes of limitation.

That which is claimed is:
 1. A method of providing electrode materialsfor a battery cell, the method comprising: preparing a high capacitynanocomposite cathode of FeF₃; preparing a high capacity nanocompositeanode of Cu and Si by: creating a Cu: Si interface via electrodepositionor physically forming Cu around Si by milling; and annealing to enhanceatomic intermixing; and combining the high capacity nanocompositecathode with the high capacity nanocomposite anode for a high energydensity Lithium-ion battery cell.
 2. The method of claim 1, whereinpreparing the high capacity nanocomposite cathode comprises: reactingiron nitrate nonahydrate with hydrofluoric acid to yield hydrated ironfluoride; and heating the hydrated iron fluoride in argon.
 3. The methodof claim 1, wherein preparing the high capacity nanocomposite cathodecomprises preparing the high capacity nanocomposite cathode of FeF₃ incarbon pores by: preparing a nanoporous carbon precursor; employingelectrochemistry or solution chemistry deposition to deposit Feparticles in the carbon pores; reacting nano Fe with liquid hydrofluoricacid to form nano FeF₃ in carbon; and milling to achieve a desiredparticle size.
 4. The method of claim 3, wherein preparing the highcapacity nanocomposite cathode further comprises characterizing theelectrochemical and/or morphological properties of the resultantmaterial.
 5. The method of claim 3, wherein milling to achieve thedesired particle size comprises mechanical milling or ball milling todecrease particle size.
 6. The method of claim 3, wherein employingelectrochemistry or solution chemistry deposition to deposit Feparticles in the carbon pores comprises: infiltrating the carbon poreswith an Fe precursor solution; and applying heat treatment in an inertatmosphere to leave behind nano Fe particles in the carbon pores.
 7. Themethod of claim 6, wherein applying heat treatment comprises heattreating the infiltrated carbon pores at a temperature of about 600 toabout 1000 degrees C. to yield Fe filled pores in a carbon host.
 8. Themethod of claim 3, wherein employing electrochemistry or solutionchemistry deposition to deposit Fe particles in the carbon porescomprises: applying heat treatment in an inert atmosphere to formnanoporous carbon; and electrochemically depositing Fe in nanopores ofcarbon.
 9. The method of claim 8, wherein applying heat treatmentcomprises heat treating the porous carbon precursor at a temperature ofabout 600 to about 1000 degrees C. in the inert atmosphere to yield ananoporous carbon host.
 10. The method of claim 3, wherein creating theCu: Si interface via electrodeposition or physically forming Cu aroundSi by milling comprises: preparing amorphous silicon nanoparticles usinghigh energy mechanical milling; placing Si powder that aggregates in afine metal mesh container; and electrodepositing a thin film of Cu onthe Si powder.
 11. The method of claim 10, further comprisingcharacterizing electrochemical and morphological properties of resultantmaterial.
 12. The method of claim 3, wherein creating the Cu: Siinterface via electrodeposition or physically forming Cu around Si bymilling comprises: providing Si powder, Cu powder, and a milling agentin a plurality of weight ratios; and milling the Si powder, Cu powder,and the milling agent via high energy mechanical milling to in-situ forma high quality Cu: Si nanocomposite.
 13. The method of claim 12, furthercomprising characterizing electrochemical and morphological propertiesof resultant material.
 14. A method of preparing a high capacitynanocomposite cathode of FeF₃ in carbon pores, the method comprising:preparing a nanoporous carbon precursor; employing electrochemistry orsolution chemistry deposition to deposit Fe particles in the carbonpores; reacting nano Fe with liquid hydrofluoric acid to form nano FeF₃in carbon; and milling to achieve a desired particle size.
 15. Themethod of claim 14, further comprising characterizing theelectrochemical and/or morphological properties of the resultantmaterial.
 16. The method of claim 14, wherein milling to achieve thedesired particle size comprises mechanical milling or ball milling todecrease particle size.
 17. The method of claim 14, wherein employingelectrochemistry or solution chemistry deposition to deposit Feparticles in the carbon pores comprises: infiltrating the carbon poreswith an Fe precursor solution; and applying heat treatment in an inertatmosphere to leave behind nano Fe particles in the carbon pores. 18.The method of claim 14, wherein employing electrochemistry or solutionchemistry deposition to deposit Fe particles in the carbon porescomprises: applying heat treatment in an inert atmosphere to formnanoporous carbon; and electrochemically depositing Fe in nanopores ofcarbon.